A quantum chemistry approach to linear vibro-polaritonic IR spectra with

perturbative electron-photon correlation

Eric W. Fischer,1, 2, ∗ Jan A. Syska,2 and Peter Saalfrank2, 3, †
1
Institut für Chemie, Humboldt-Universität zu Berlin,
Brook-Taylor-Straße 2, D-12489 Berlin, Germany
2
Institut für Chemie, Universität Potsdam, Karl-Liebknecht-Straße 24-25, D-14476 Potsdam-Golm, Germany
3
Institut für Physik und Astronomie, Universität Potsdam,
Karl-Liebknecht-Straße 24-25, D-14476 Potsdam-Golm, Germany
(Dated: January 5, 2024)
arXiv:2401.02188v1 [physics.chem-ph] 4 Jan 2024

In the vibrational strong coupling (VSC) regime, molecular vibrations and resonant low-frequency
cavity modes form light-matter hybrid states, named vibrational polaritons, with characteristic IR
spectroscopic signatures. Here, we introduce a quantum chemistry based computational scheme for
linear IR spectra of vibrational polaritons in polyatomic molecules, which perturbatively accounts
for nonresonant electron-photon interactions under VSC. Specifically, we formulate a cavity Born-
Oppenheimer perturbation theory (CBO-PT) linear response approach, which provides an approxi-
mate but systematic description of such electron-photon correlation effects in VSC scenarios, while
relying on molecular ab initio quantum chemistry methods. We identify relevant electron-photon
correlation effects at second-order of CBO-PT, which manifest as static polarizability-dependent
Hessian corrections and an emerging polarizability-dependent cavity intensity component providing
access to transmission spectra commonly measured in vibro-polaritonic chemistry. Illustratively, we
address electron-photon correlation effects perturbatively in IR spectra of CO2 and Fe(CO)5 vibro-
polaritonic models qualitatively in sound agreement with non-perturbative CBO linear response
theory.

Introduction.— Vibrational polaritons are light-matter monic approximation for molecular and cavity modes in
hybrid states formed when molecular vibrational modes combination with a linear approximation for the ground
strongly interact with quantized modes of optical low- state dipole moment. This is particularly beneficial for
frequency cavities[1] lying at the heart of the emerging treating vibrations and spectra of large molecules or
field of vibro-polaritonic chemistry[2, 3]. Experimen- molecular ensembles quantum mechanically, since only
tally, vibrational polaritons exhibit characteristic spec- Hessians and linearized dipole moments at equilibrium
troscopic signatures, specifically transitions to upper and structures are required.
lower vibro-polaritonic states, which have been probed by
both linear[4–9] and non-linear[10] infrared (IR) spectro-
scopic techniques.
Computationally, vibro-polaritonic IR spectra are
commonly obtained from linear response theory, where
two distinct routes exist: First, linear response ap-
proaches based on effective ground state Pauli-Fierz
Hamiltonians, which are fully characterized by purely
molecular properties such as the molecular ground state
potential energy surface (PES) and dipole moment, eas-
ily accessible by means of standard quantum chem-
istry methods.[11–14] Second, a linear response approach
formulated in the cavity Born-Oppenheimer (CBO)
approximation[15–18], which relies on an extended elec-
tronic structure problem taking into account nonreso-
nant interactions between electrons and low-frequency
FIG. 1. Sketch of CO2 and Fe(CO)5 vibro-polaritonic model
cavity modes inducing electron-photon correlation.[18]
systems studied with respect to their linear IR response in
The CBO formulation is more complete but also more in- this work.
volved, since both generalized cavity PES and dipole mo-
ments depend on both molecular and cavity coordinates.
Recently, we showed that effective ground state and
From a linear response perspective, both approaches are
CBO formulations differ in the way they account for
formulated in double-harmonic approximation, i.e., har-
electron-photon correlation.[19] Specifically, the effective
ground state formulation can be understood as additional
approximation to the CBO formulation, which we named
∗ ericwfischer.sci@posteo.de crude CBO approximation, that fully neglects electron-
† peter.saalfrank@uni-potsdam.de photon correlation in the VSC regime.[19] The nonres-
 2

onant nature of interactions between electrons and low- constitutes the light-matter interaction potential
frequency cavity modes characterized by distinct exci- 2Nc 2N
tation energy scales of both subsystems, subsequently g02 Xc
(eλk · den )2 , (3)
X
Wc = g0 ωk (eλk · den ) xλk +
motivated us to propose a perturbative connection be- 2
λ,k λ,k
tween crude CBO and correlated CBO formulations, de-
noted as CBO perturbation theory (CBO-PT).[19] CBO- with light-matter interaction linear in the coupling con-
PT solves the extended CBO electronic structure prob- stant, g0 , and dipole self-energy (DSE) quadratic in
lem perturbatively and allows for a systematic correc- g0 .[24] The coupling constant, g0 = √ǫ 1V , is only de-
0 cav
tion of electron-photon correlation in the crude CBO termined by the cavity volume, Vcav , and the permit-
approach.[19] Further, CBO-PT is conceptually similar tivity, ǫ0 . It p
relates to a mode specific coupling con-
to other perturbative approaches[20, 21], which however stant, gk = 2ωk /~ g0 (cf. Supplementary Informa-
constitute a further approximation[19, 20] or do not rely tion (SI), Sec.S1). The light-matter interaction, Wc , in
on the CBO formulation[21]. Eq.(3) is mediated by the polarization-projected molec-
Here, we introduce an approximation to the non- ular dipole operator, eλk · den , with cavity polariza-
perturbative CBO linear response framework of Bonini tion vector, eλk . Thus, Wc couples the electronic sub-
and Flick[15] by combining CBO-PT with linear re- system to low-frequency cavity modes and additionally
sponse theory. This approach allows us to systemat- induces electron-electron interactions due to the DSE
ically correct vibro-polaritonic IR spectra for electron- term.[15, 18, 19] In the non-interacting limit with g0 = 0,
photon correlation effects while fully relying on molecu- the light-matter interaction, Wc , vanishes such that,
lar properties, which are accessible by ab initio quantum Ĥec = Ĥe +Vc , and Eq.(1) reduces to the electronic TISE
chemistry methods. We derive explicit expressions for with a constant energy shift induced by the cavity poten-
electron-photon correlation corrected vibro-polaritonic tial, Vc .
Hessian matrix elements and IR intensities, which are In CBO linear response theory, the ground state cPES
both shown to be determined by the molecule’s static po- in Eq.(1) is harmonically approximated[15]
larizability, whose possible relevance has been noted only
recently.[21–23] We illustratively apply the CBO-PT lin- (ec) (ec) 1 T (ec)
E0 (R, x) ≈ E0 (R0 , x0 ) + C H0 C , (4)
ear response approach to vibro-polaritonic model systems 2
of CO2 and Fe(CO)5 (cf. Fig.1) in line with Ref.[15], and around a minimum configuration, (R0 , x0 ), of the cPES
discuss electron-photon correlation effects in connection
with coordinate vector, C = (R̃, x), which collects Nvib
to experimentally relevant transmission spectra[4, 7].
CBO Linear Response Theory.— We first recapitu- mass-weighted
√ cartesian displacement coordinates, R̃i =
late the main aspects of CBO linear-response theory[15], Mi Ri , with atomic mass, Mi , and 2Nc cavity dis-
which fully accounts for electron-photon correlation in placement coordinates, x. The vibro-polaritonic Hessian,
vibro-polaritonic IR spectra. We consider a molecular H (ec)
0
, contains second-order derivatives of the cPES with
system with Nn nuclei under VSC with 2Nc quantized respect to both mass-weighted molecular cartesian and
transverse field modes of an IR cavity. We further- cavity displacement coordinates. It specifies a matrix
more assume the CBO approximation to be valid, i.e., eigenvalue problem[15]
non-adiabatic coupling to the excited state manifold is  (ec)
H QQ H (ec)

qm qm
! !
negligible.[18, 19] The CBO electronic ground state prob- QC 2
  = Ωm . (5)
lem is described by an electron-photon time-independent H (ec) H (ec)
c c
QC CC m m
Schrödinger equation (TISE)[17, 18]
(ec)
Ĥec |Ψ0
(ec)
(R, x)i = E0
(ec)
(R, x) |Ψ0 (R, x)i , (1) where H (ec)
0
is written as 2 × 2-block matrix with molec-
ular (QQ), cavity (CC) and light-matter interaction
(ec) blocks (QC), respectively. Eigenvectors, (q m , cm )T , re-
with adiabatic electron-photon ground state, |Ψ0 i, and
ground state cavity potential energy surface (cPES), semble vibro-polaritonic normal modes with molecular,
(ec)
E0 , which parametrically depend on both nuclear, R, q m , and cavity components, cm , characterized by cor-
and cavity displacement coordinates, x. The electron- responding harmonic vibro-polaritonic frequencies, Ωm .
photon Hamiltonian reads[18] The eigensystem of Eq.(5) provides access to linear vibro-
polaritonic IR spectra
Ĥec = Ĥe + Vc + Wc , (2) Np
X
with electronic Hamiltonian, Ĥe = T̂e + Vcoul , composed σIR (~ω) = Im δ(~ω − ~Ωm ) , (6)
of the electronic kinetic energy, T̂e , and the molecular m
P2N
Coulomb potential, Vcoul . Further, Vc = 21 λ,kc ωk2 x2λk , for Np = Nvib + 2N
Pc vibro-polaritonic normal modes. IR
is the harmonic cavity potential characterized by har- intensities, Im = κ |Zκm |2 , are determined by cartesian
monic frequencies, ωk , and displacement coordinates, components of mode effective charges
xλk , with polarization, λ, and mode index, k, respec- (Q) (C)
tively. The third term on the right-hand side of Eq.(2) Zκm = Zκm + Zκm , κ = x, y, z , (7)
 3

with molecular and cavity mode contributions[15] here given in block-matrix form in analogy to Eq.(5).
We restrict our discussion to perturbation order n ≤ 2,
N (ec)
X vib
∂D00,κ i.e., up to CBO-PT(2), sufficient to capture leading-
(Q)
Zκm = qmi , (8) order electron-photon correlation corrections[19]. In
∂ R̃i
i contrast to the non-perturbative CBO approach[15],
2Nc (ec) we work directly in a representation employing mass-
(C)
X ∂D00,κ
Zκm = cmλk , (9) weighted molecular normal modes, which constitute the
∂xλk
λ,k CBO-PT(0) reference and relate to coordinates, Q =
(Q1 , . . . , Qvib ). Note, molecular normal modes are not
where, qmi and cmλk , resemble elements of q m and cm in strictly extractable from Eq.(5) due to light-matter inter-
Eq.(5), respectively. The IR intensity of the mth-vibro- action unless g0 = 0. Linear vibro-polaritonic IR spectra
polaritonic transition decomposes via Eq.(7) into in CBO-PT(n) are given by
Xh i
Np
(Q) 2 (C) 2 (Q) (C)
Im = (Zκm ) + (Zκm ) + 2Zκm Zκm , (10) (n)
X
(n)
κ
σIR (~ω) = Im δ(~ω − ~Ω(n)
m ) , (14)
m
such that vibro-polaritonic IR spectra, σIR , exhibit a
(Q) (C) with approximate vibro-polaritonic normal-mode fre-
molecular, σIR , a cavity, σIR , and an additional mixed (n) (n) P (n) 2
(X) quencies, Ωm , and IR intensities, Im = κ |Zκm | ,
contribution, σIR , respectively. Further, Zκm is deter- (n) (Q,n) (C,n)
(ec) with, Zκm = Zκm + Zκm . The approximate mode
mined by cartesian components, D00,κ , of a generalized (n)
effective charge, Zκm , is determined by components (cf.
permanent dipole moment SI, Sec.S1A for derivation)
(ec) (ec) (ec)
D00 (R, x) = hΨ0 (R, x)|den |Ψ0 (R, x)ir , (11) N
X vib
r (n)
~ ∂D00,κ
(Q,n)
Zκm = qmi , (15)
which is evaluated with respect to the electron-photon i
2ωi ∂Qi
(ec) 2Nc (n)
ground state, |Ψ0 i, where integration over electronic
r
(C,n)
X ~ ∂D00,κ
coordinates is indicated by h. . .ir . Zκm = cmλk , (16)
2ωk ∂xλk
Perturbative CBO Linear Response Theory.— We λ,k
now introduce a systematic approximation to the CBO
which result from a linearization of the approximate gen-
linear response approach[15] based on cavity Born-
eralized permanent dipole moment in the normal mode
Oppenheimer perturbation theory (CBO-PT)[19]. CBO-
representation
PT approximates nonresonant interactions between elec-
trons and low-frequency cavity modes and therefore (n)
D00 (R, x) = hΦ0
(n−1)
(R, x)|den |Φ0
(n−1)
(R, x)ir . (17)
electron-photon correlation by treating the light-matter
interaction potential, Wc , in Eq.(3) as perturbation of The latter expression is determined by the perturbatively
the electronic subsystem[19] approximated adiabatic electron-photon ground state,
(n−1) Pn−1 k (k)
|Φ0 i = k=0 λ |Ψ0 i (cf. SI, Sec.S1). Note, in
Ĥec = Ĥ0 + λ Wc , (12) (Q,n) (C,n)
contrast to Eq.(7), both Zκm and Zκm depend on
prefactors with molecular normal mode, ωi , and cavity
with zeroth-order Hamiltonian, Ĥ0 = Ĥe + Vc , and for-
frequencies, ωk , which follow from the normal mode rep-
mal perturbation parameter, λ. In Ĥ0 , the cavity po-
resentation (cf. SI, Sec.S1A).
tential, Vc , is a constant with respect to the bare elec-
We now provide explicit expressions for Hessian matrix
tronic problem, such that zeroth-order states are given
(e) elements and IR intensities up to CBO-PT(2) as derived
by bare adiabatic electronic states, |Ψµ i. CBO-PT is in SI, Sec.S1. The sum of CBO-PT(0) and CBO-PT(1)
motivated by distinct excitation energy scales of elec- Hessians, which do not account for electron-photon cor-
tronic and low-frequency cavity mode subsystems, and relation, is determined by elements (cf. SI, Sec.S1B and
provides a systematic approximation of electron-photon S1C)
correlation in light-matter hybrid systems under VSC by
perturbatively solving the electron-photon TISE (1).[19]   2
(i) (j)
X
At nth-order of CBO-PT, abbreviated as CBO-PT(n), H (0)
QQ
+ H (1)
QQ
= ωi2 δij + g02 Nc dλ dλ , (18)
(ec) Pn (k) ij
the approximate cPES reads, E0 ≈ k=0 λk E0 (cf.  
λ
(i)
SI, Sec.S1), which straightforwardly leads to the corre- H (0)
QC
+ H (1)
QC i,λk
= g0 ωk dλ , (19)
sponding Hessian  
 (k) H (0) + H (1)
= ωk2 δkk′ δλλ′ . (20)
H QQ H (k) CC CC

n λk,λ k
′ ′
X QC
H (ec)
0
≈   , (13) Here, the DSE term induces inter-normal-mode couplings
(k) (k)
k=0 H H
QC CC in Eq.(18). Light-matter interaction elements in Eq.(19)
 4

relate to polarization-projected permanent dipole mo- which contains both molecular and cavity contributions
(i) with dipole derivatives explicitly given by (cf. SI Sec.S3)
ment derivatives, dλ = ∂Qi (eλ · d00 ) |Qi =0 . We assume
here identical polarization vectors for all modes with in- (Q,2) 2
(1)
dex, k. The CBO-PT(1) IR spectrum, σIR , is fully de- ∂D00,κ (i) g2 X (i)
= d00,κ − 0 Nc α0κλ dλ , (29)
termined by the zeroth-order adiabatic electronic ground ∂Qi 2
λ
(e) (1)
state, |Ψ0 i, such that, D00 = d00 in Eq.(17) with first- (C,2)
∂D00,κ
order IR intensity given by = −g0 ωk α0κλ . (30)
X ∂xλk
(Q,1) (Q,1) 2
Im = |Zκm | , (21) (2)
κ
with second-order dipole moment, D00 , following from
(2)
N vib
r Eq.(17). Note, in the non-interacting limit, qmi = δmi
(Q,1)
X ~ ∂d00,κ (1) (C,2)
Zκm = q , (22) ∂D
and ∂x00,κ = 0, such that the CBO-PT(2) IR spectrum
i
2ωi ∂Qi mi λk
reduces to the molecular spectrum. In Eq.(29) and (30),
which reduces in the non-interacting limit with g0 = 0 to we find a static polarization-dependent correction of the
(1)
qmi = δmi and the molecular intensity, Im
(Q,1) (Q,1)
= Ii . molecular intensity and in particular a non-vanishing cav-
Notably, in CBO-PT(1) the vibro-polaritonic IR spec- ity component, which is determined by the light-matter
trum is fully determined by molecular intensity com- interaction strength, g0 , and the static polarizability,
(Q,1) α0κλ , of the molecular subsystem. Notably, the related
ponents, Im , since the cavity mode effective charge (C,2)
(C,1) cavity dipole component, D00,κ , is linear in g0 and xλk
vanishes, Zκm = 0. Thus, vibro-polaritonic contribu-
tions enter only via cavity-induced linear combinations of (cf. SI, Sec.S3) in agreement with numerical results re-
(1) ported for non-perturbative CBO linear response theory
molecular normal mode components, qmi , and the CBO-
(1) under VSC (cf. supporting information of Ref.[15]) In
PT(1) IR spectrum, σIR , exclusively probes the effective contrast to CBO-PT(1), the non-vanishing CBO-PT(2)
matter response of the light-matter hybrid system under cavity intensity component allows for addressing trans-
VSC. Further, CBO-PT(2) Hessian matrix element cor- mission spectra, which exclusively probe the cavity re-
rections in Franck-Condon approximation are given by (C)
sponse, σIR , of the light-matter hybrid system com-
(cf. SI, Sec.S1D and S2) monly measured in vibro-polaritonic chemistry.[4, 7, 8]
2 In this context, we like to emphasize, that Eq.(30) solely
  g04 2 X (i) 0 (j) emerges due to the fact that we (perturbatively) account
H (2) = − N dλ αλλ′ dλ′ , (23)
QQ ij 4 c for electron-photon correlation effects in the description
′ λ,λ
2
of the vibro-polaritonic system by exclusively relying on
  g03 X (i) molecular ground state information. The latter is ob-
H (2) =− ωk Nc α0λλ′ dλ′ , (24)
QC i,λk 2 tainable from standard quantum chemistry with polariz-
′ λ
  abilities being practically accessible by means of response
H (2)
CC
= −g02 ωk ωk′ α0λλ′ , (25) theory.
λk,λ′ k′
IR spectra under VSC. — In the remainder of this
which are all determined by polarization-projected work, we discuss IR spectra of CO2 and Fe(CO)5 vibro-
ground state (superscript 0) static polarizability ten- polaritonic models[15] obtained from second-order CBO-
sor elements, α0λλ′ . Notably, the leading-order correc- PT linear response theory with a focus on electron-
tion in Eq.(25) enters the cavity block and exhibits a photon correlation effects. We consider polarization-
matter-induced perturbative coupling of distinct cavity averaged vibro-polaritonic IR spectra
modes[19] in agreement with non-perturbative CBO lin- K
ear response theory[15]. (n) 1 X (n)
σ̄IR (~ω) = σ (~ω) , n = 0, 1, 2 , (31)
(2)
The CBO-PT(2) IR spectrum, σIR (~ω), is determined K α α
(2)
by second-order vibro-polaritonic frequencies, Ωm , and to mimic random molecular orientation, where the sum
intensities derived from second-order mode effective runs over all unique polarization components, α = x, y, z,
charges as with K = 1, 2, 3, depending on the number of contribut-
(2)
X
(2) 2 ing terms. Molecular structures, harmonic frequencies,
Im = |Zκm | , (26) dipole derivatives and static polarizability tensors ele-
κ
ments are obtained from density functional theory (DFT)
N r (Q,2)
(Q,2)
X vib
~ ∂D00,κ (2) using the TPSSh[25, 26] and B3LYP[27] functionals and
Zκm = qmi , (27) a Def2TZVP basis set[28, 29]. Computational details
i
2ωi ∂Qi
are provided in SI, Sec.S4A. We furthermore consider
2Nc (C,2)
spontaneous emission-induced Lorentzian peak broaden-
r
(C,2)
X ~ ∂D00,κ (2)
Zκm = c , (28) ing (and neglect other dissipative channels) with FWHM,
2ωk ∂xλk mλk
λ,k κ = 41 cm−1 (cf. SI, Sec.S4B) for an experimentally
 5

FIG. 2. Linear vibro-polaritonic

√ IR spectra for selected single-molecule models under VSC with a single cavity mode at coupling
strength, g0 = 0.03 Eh /ea0 . Top-row: z-polarized IR spectra of the antisymmetric CO2 -stretching mode under VSC with
(1) (2)
a single cavity mode, ~ωc = ~ωas = 2400 cm−1 , with a) CBO-PT(1) and CBO-PT(2) IR spectra, σIR (~ω) and σIR (~ω),
(0) (Q,2) (C,2)
besides bare molecular spectrum, σIR (~ω), b) molecular, cavity and mixed CBO-PT(2) contributions, σIR (~ω), σIR (~ω)
(X,2) (2) (C,2)
and σIR (~ω) and c) comparison of normalized σIR (~ω) and σIR (~ω). Bottom-row: Polarization-averaged linear vibro-
polaritonic IR spectra for the CO-stretch band of a single Fe(CO)5 molecule under VSC with a single cavity mode, ~ωc =
~ωe′ = 2052 cm−1 with d)-f) providing same information as a)-c). Stick spectra in d) resemble individual polarization-dependent
(2)
contributions to σ̄IR (cf. main text for details). The respective cavity mode frequency is indicated by a grey vertical line in all
panels.

motivated cavity quality factor, Q = ~ω κ [30, 31], with

c
Q = 50 (CO2 ) and Q = 59 (Fe(CO)5 ).[8]
CO2 under VSC.— We first discuss the antisymmet-
ric stretching mode of CO2 strongly coupled to a sin-
gle resonant cavity mode, ~ωc = ~ωas , with ~ωas =
2400 cm−1 √ (TPSSh/Def2TZVP) at coupling strength,
g0 = 0.03 Eh /ea0 . Here, the IR spectrum reduces
(n) (n)
to, σIR (~ω) = σz (~ω), since only the dipole compo-
nent along the molecular z-axis contributes. In Fig.2a,
CBO-PT(1) and CBO-PT(2) IR spectra are shown for
CO2 under VSC besides the bare molecular spectrum,
(0)
σIR (~ω). We observe a Rabi-splitting characterized by
lower and upper vibro-polaritonic transitions for both
CBO-PT(1) and CBO-PT(2). Uncorrelated CBO-PT(1)
spectra exhibit nearly identical molecular and photonic
contributions for both polariton states, contrasted by
a dominantly photonic lower and dominantly molecular
upper polariton state in correlated CBO-PT(2) spectra
in agreement with non-perturbative CBO results[15] (cf.
SI, Sec.S4B). Further, the correlated CBO-PT(2) spec-
trum exhibits a pronounced peak asymmetry in favour
of the lower polariton transition, a spectral red-shift and
a pronounced asymmetric peak splitting relative to the
(1)
cavity frequency. Rabi splittings, ΩR = 121 cm−1 and
(2)
ΩR = 134 cm−1 , indicate a slightly stronger effective
light-matter interaction in presence of electron-photon
correlation, despite the fact that both results have been
obtained at identical light-matter coupling.
We now turn to the details of the CBO-PT(2) IR
spectrum, Fig.2b, where we compare molecular, σIR ,
(Q,2)
(C,2) (X,2)
cavity, σIR , and mixed contributions, σIR , following
(Q,2)
from Eq.(10). Although, σIR is dominant relative to
(C,2) (X,2) (2)
σIR , σIR determines the peak asymmetry of σIR by
“shifting” intensity from the upper to the lower vibro-
polaritonic transition. This effect directly translates to
the sign of the photonic contribution in linear combina-
tions forming upper (+) and lower (-) polariton states

FIG. 3. Linear vibro-polaritonic IR spectra for CO2 ensemble models under VSC with a single cavity mode, ~ωc = ~ωas =
2400 cm−1 . a) Ensemble and effective CBO-PT(n) IR spectra, σens (~ω) and σeff (~ω) for n =, 1, 2, b) molecular, cavity and
(Q,2) (C,2)
mixed CBO-PT(2) contributions, σens (~ω), σens (~ω) and σens (~ω) for explicit ensemble and c) comparison of normalized
(2) (C,2)
σens (~ω) and σens (~ω) for explicit ensemble. The respective cavity mode frequency is indicated by a grey vertical line.
(cf. SI, Sec.S4B): Mixed intensity contributions satisfy,
I∓
(X,2) (Q,2) (C,2)
∝ ±|Zκ∓ ||Zκ∓ |, since the dipole derivative in
(C,2)
Eq.(30) determining Zκ∓ is negative. Further, we recall
that IR transmission spectra of vibro-polaritonic systems
measured in micro-fluidic optical cavities probe the cav-
ity response of the light-matter hybrid system.[4, 7, 8]
The cavity response translates here into the cavity com-
(C,2)
ponent, σIR , which appears in CBO-PT(2) but is not
accounted for in uncorrelated CBO-PT(1) models[15]. In
Fig.2c, we compare full and cavity CBO-PT(2) IR spec-
tra, where the intensity has been normalized for reasons
of comparison. We find nearly identical results with only
minor intensity deviations for the lower polariton peak
in the spectral region of interest. However, when the full
(2)
IR spectrum is considered, then σIR still contains molec-
ular contributions related to CO2 bending modes at low
frequencies (cf. SI, Sec.S4B). Those peaks are absent in
(C,2)
σIR since bending modes do not couple to the “high
frequency” cavity mode.
Fe(CO)5 under VSC.— As a second example, we dis-
cuss the CO-stretch band of Fe(CO)5 under VSC, which
constitutes a both experimentally and theoretically rele-
vant molecular multi-mode example.[8, 15, 32] The CO-
stretch band decomposes into a doubly-degenerate equa-
torial normal mode (symmetry e′ in molecular point
group D3h ) and a single axial normal mode (a′′2 in
D3h ) with harmonic frequencies, ~ωe′ = 2052 cm−1 and
~ωa′′2 = 2078 cm−1 (TPSSh/Def2TZVP, cf. SI, Sec.S4A).
We consider a single cavity mode tuned resonant to the
equatorial e′ -modes,
√ ~ωc = ~ωe′ , at light-matter inter-
action, g0 = 0.03 Eh /ea0 . Here, e′ -modes are (x, z)-
polarized, while the a′′2 -mode is y-polarized. Therefore,
all three molecular modes can enter VSC depending on
the cavity mode polarization, which constitutes a sce-
nario with both strongly coupled and decoupled molecu-
lar modes. In Fig.2d, polarization-averaged CBO-PT(1)
6
(n) (n)
(X,2)
and CBO-PT(2) IR spectra are shown besides the bare
molecular CBO-PT(0) spectrum. Note, the a′′2 -peak in
the latter is only visible as blue-shifted shoulder relative
to the dominant transition for the herein chosen peak
broadening. Further, we display CBO-PT(2) stick spec-
tra to highlight the polarization-dependence of the in-
dividual spectral contributions. According to the aver-
aged character, we only discuss effective polaritonic sig-
natures resulting from broadening effects. We find the
e′ -peak to split under VSC but in contrast to CO2 , we
find here additionally a pronounced molecular contribu-
tion related to uncoupled molecular modes. Note, those
do not refer to “dark states” as present in the ensem-
ble scenario below. The correlated CBO-PT(2) IR spec-
trum exhibits a strong red-shift and significantly more
intense peaks relative to the uncorrelated CBO-PT(1)
result. Both share a slight peak asymmetry in favour
of the upper polariton peak. Further, a comparison of
(1) (2)
Rabi splittings, ΩR = 169 cm−1 and ΩR = 228 cm−1 ,
indicates also here an enhanced effective light-matter in-
teraction in presence of electron-photon correlation. By
(2) (Q,2) (C,2) (X,2)
analysing, σ̄IR , in terms of, σ̄IR , σ̄IR and σ̄IR , re-
veals a trend similar to the CO2 example (cf. Fig.2e):
(Q,2) (C,2)
σ̄IR is the dominant contribution relative to σ̄IR , but
the cross term again “shifts” intensity from the upper
to the lower vibro-polaritonic transition. Importantly,
(Q,2)
in contrast to the CO2 example, σ̄IR contains here in
addition to the matter response of the light-matter hy-
brid system bare molecular contributions, which relate
to uncoupled CO-stretching modes. In order to access
the light-matter response without bare molecular con-
(2)
tributions, we compare normalized, σ̄IR and σ̄IR , in
(C,2)
Fig.2f: Here, we find the upper polariton peak to signifi-
(C,2)
cantly differ in intensity for σ̄IR , which directly relates
to the absence of additional molecular contributions of
(2)
uncoupled CO-modes present in σ̄IR . Thus, correlation

corrected CBO-PT(2) IR spectra allow for avoiding arti-
ficial molecular intensity contributions related to uncou-
pled molecular modes in vibrational multi-mode systems
under VSC, which are not probed in vibro-polaritonic
transmission spectroscopy.[4, 7, 8]
Collective VSC effects in CO2 ensembles.— We finally
address collective strong coupling effects in two different
molecular ensemble models of CO2 under VSC (cf. SI,
Sec.5), which have also been studied in Ref.[15]: First,
an explicit ensemble of M molecules in the dilute gas
limit[33], which interact only via√DSE contributions at
light-matter coupling, g0 = 0.01 Eh /ea0 . Second, an
effective “ensemble” model, which contains a single CO2
molecule under VSC with a single cavity mode char-
acterized
√ by an effective enhanced interaction constant, (n)
geff = M g0 . In Fig.3a, we compare ensemble, σens ,
(n)
and effective IRspectra, σeff , for CBO-PT(1) and CBO-
PT(2) for M = 20 parallel aligned CO2 molecules. In-
tensities have been scaled by a factor of M −1 for rea-
sons of comparison. We find an excellent agreement be-
tween spectra obtain at both levels of CBO-PT in agree-
ment with Ref.[15]. Further, for the ensemble model,
we observe qualitatively identical results for the different
(2)
spectral contributions to σens in Fig.3b as in the single-
molecule model discussed in Fig.(2)b. In addition, both
the full IR spectrum and the bare cavity response are
very similar with a minor intensity mismatch for the up-
per polariton peak (cf. Fig.3c). We like to note here
that the explicit ensemble hosts M − 1 “dark states”
with vanishing intensity at the bare molecular frequency,
~ωas = ~ωc , which resemble purely molecular linear com-
binations of all CO2 vibrations participating in VSC and
are to be contrasted by uncoupled molecular states with
non-vanishing intensity in the IR spectrum of Fe(CO)5
under VSC. From the ensemble analysis, we conclude
that transmission spectra obtained from CBO-PT linear
response theory can be calculated via effectively scaled
single-molecule approaches subject to
√ an effective light-
matter interaction constant, geff = M g0 , when inter-
molecular interactions are neglected in the ensemble in
line with the non-perturbative CBO approach[15].
Conclusions.— We introduced a cavity Born-
Oppenheimer perturbation theory (CBO-PT) linear
response approach to calculate electron-photon correla-
tion corrected vibro-polaritonic IR spectra of polyatomic
molecules under VSC. This approach approximates
non-perturbative CBO linear response theory[15] by
perturbatively approximating nonresonant interactions
between electrons and low-frequency cavity modes, while
fully relying on molecular ab initio quantum chemistry
methods. In zeroth-order, we obtain the bare molecular
spectrum and in first-order the linear vibro-polaritonic
IR spectrum in absence of electron-photon correla-
tion. Electron-photon correlation is accounted for at
second-order of CBO-PT linear response theory, where
it manifests as static polarizability-dependent cavity
intensity component and related corrections of Hessian
matrix elements, most notably a matter-mediated
7
inter-cavity mode coupling. Those corrections capture
the main characteristics of non-perturbative CBO linear
response theory[15] and provide additional physical
insight due to their explicit relation to molecular and
cavity mode properties. A comparison of uncorrelated
CBO-PT(1) and correlation corrected CBO-PT(2) IR
spectra for CO2 and Fe(CO)5 vibro-polaritonic models
reveals the impact of electron-photon correlation on
vibro-polaritonic intensity ratios, Rabi splittings and
experimentally relevant transmission spectra, which
probe only the cavity response of the light-matter
hybrid system. In both model scenarios, CBO-PT(2)
linear response theory exhibits significant qualitative
agreement with non-perturative CBO linear response
results reported in Ref.[15]. In summary, CBO-PT
linear response theory constitutes a promising since
easily accessible approach to vibro-polaritonic IR spectra
of polyatomic molecular systems under VSC accounting
for non-trivial electron-photon correlation effects. A
systematic quantitative comparison of CBO-PT and
non-perturbative CBO linear response theories based on
controllable ab initio wave function approaches[16] will
be subject of future work.
ACKNOWLEDGEMENTS
The authors acknowledge funding by the Deutsche
Forschungsgemeinschaft (DFG, German Research Foun-
dation) under Germany’s Excellence Strategy within
“Sonderforschungsbereich 1636” of University Potsdam,
project A05, “Understanding and controlling reactivity
under vibrational and electronic strong coupling”. E.W.
Fischer acknowledges the kind hospitality of Michael
Roemelt and his group at Humboldt-Universität zu
Berlin, and helpful discussions with Thomas Schnap-
pinger (Stockholm). J.A. Syska acknowledges support
and funding by the International Max Planck Research
School for Elementary Processes in Physical Chemistry.
DATA AVAILABILITY STATEMENT
The data that support the findings of this study are
available from the corresponding author upon reasonable
request.
CONFLICT OF INTEREST
The authors have no conflicts to disclose.

[1] Ebbesen, T.W. Hybrid light-matter states in a molecular
and material science perspective. Acc. Chem. Res. 49,
2403 (2016).
[2] Hirai, K.; Hutchison, J.A.; Uji-i, H. Recent progress
in vibropolaritonic chemistry. ChemPlusChem 85, 1981
(2020).
[3] Nagarajan, K.; Thomas, A.; Ebbesen, T.W. Chemistry
under vibrational strong coupling. J. Am. Chem. Soc.
143, 16877 (2021).
[4] Shalabney, A.; George, J.; Hutchison, J.A.; Pupillo, G.;
Genet, C.; Ebbesen, T.W. Coherent coupling of molecu-
lar resonators with a microcavity mode. Nat. Commun.
6, 5981 (2015).
[5] Shalabney, A.; George, J.; Hiura, H., Hutchison, J.A.;
Genet, C.; Hellwig, P.; Ebbesen, T.W. Enhanced Raman
Scattering from Vibro-Polariton Hybrid States. Angew.
Chem., Int. Ed. 54, 7971-7975 (2015).
[6] George, J.; Shalabney, A.; Hutchison, J.A.; Genet, C.;
Ebbesen, T.W. Liquid-phase vibrational strong coupling.
J. Phys. Chem. Lett. 6, 1027 (2015).
[7] Long, J.P.; Simpkins, B.S. Coherent coupling between
a molecular vibration and Fabry-Perot optical cavity to
give hybridized states in the strong coupling limit. ACS
Photonics 2, 130 (2015).
[8] George, J.; Chervy, T.; Shalabney, A.; Devaux, E.; Hiura,
H.; Genet, C.; Ebbesen, T.W. Multiple Rabi Splittings
under Ultrastrong Vibrational Coupling. Phys. Rev. Lett.
117, 153601 (2016).
[9] Chervy, T.; Thomas, A.; Akiki, E.; Vergauwe, R.M.A.;
Shalabney, A.; George, J.; Devaux, E.; Hutchison, J.A.;
Genet, C.; Ebbesen, T.W. Vibro-polaritonic IR emission
in the strong coupling regime. ACS Photonics 5, 217
(2018).
[10] Xiang, B.; Ribeiro, R.F.; Dunkelberger, A.D.; Wang, J.;
Li, Y.; Simpkins, B.S.; Owrutsky, J.C.; Yuen-Zhou, J.;
Xiong, W. Two-dimensional infrared spectroscopy of vi-
brational polaritons. Proc. Natl. Acad. Sci. 115, 4845
(2018).
[11] Li, T. E.; Subotnik, J. E.; Nitzan, A.; Cavity molecular
dynamics simulations of liquid water under vibrational
ultrastrong coupling. Proc. Natl. Acad. Sci. 117, 18324
(2020).
[12] Fischer, E.W.; Saalfrank, P. Ground state properties and
infrared spectra of anharmonic vibrational polaritons of
small molecules in cavities. J. Chem. Phys. 154, 104311
(2021).
[13] Lieberherr, A. Z.; Furniss, S. T. E.; Lawrence, J. E.;
Manolopoulos, D. E.; Vibrational strong coupling in liq-
uid water from cavity molecular dynamics. J. Chem.
Phys. 158, 234106 (2023).
[14] Gómez, J.A.; Vendrell, O. Vibrational Energy Redistri-
bution and Polaritonic Fermi Resonances in the Strong
Coupling Regime. J. Phys. Chem. A 127, 1598 (2023).
[15] Bonini, J.; Flick, J. Ab initio linear-response approach
to vibro-polaritons in the cavity Born-Oppenheimer ap-
proximation. J. Chem. Theory Comput. 18, 2764 (2022).
[16] Schnappinger, T.; Kowalewski, M. Ab-Initio Vibro-
Polaritonic Spectra in Strongly Coupled Cavity-Molecule
Systems. J. Chem. Theory Comput. 19, 9278 (2023).
[17] Flick, J.; Ruggenthaler, M.; Appel, H.; Rubio, A. Atoms
and molecules in cavities, from weak to strong coupling in
8
quantum-electrodynamics (QED) chemistry. PNAS 114,
3026 (2017).
[18] Flick, J.; Appel, H.; Ruggenthaler, M.; Rubio, A.
Cavity Born-Oppenheimer approximation for correlated
electron-nuclear-photon systems. J. Chem. Theory Com-
put. 13, 1616, (2017).
[19] Fischer, E.W.; Saalfrank, P. Beyond Cavity Born-
Oppenheimer: On Nonadiabatic Coupling and Effective
Ground State Hamiltonians in Vibro-Polaritonic Chem-
istry. J. Chem. Theory Comput. 19, 7215-7229 (2023).
[20] Galego, J.; Climent, C; Garcia-Vidal, F.J.; Feist, J. Cav-
ity Casimir-Polder forces and their effects in ground-state
chemical reactivity. Phys. Rev. X 9, 021057 (2019).
[21] Szidarovszky, T. An efficient and flexible approach for
computing rovibrational polaritons from first principles.
arXiv preprint arXiv:2304.02346 (2023).
[22] Haugland, T. S.; Philbin, J. P.; Ghosh, T. K.; Chen,
M.; Koch, H.; Narang, P. Understanding the polaritonic
ground state in cavity quantum electrodynamics. arXiv
preprint arXiv:2307.14822 (2023).
[23] Schäfer, C.; Fojt, J.; Lindgren, E., Erhart, P. Machine
Learning for Polaritonic Chemistry: Accessing chemical
kinetics. arXiv preprint arXiv:2311.09739 (2023).
[24] The interaction parameter g0 is equivalent to λc em-
ployed by Bonini and Flick.
[25] Tao, J. M.; Perdew, J. P.; Staroverov, V. N.; Scuseria,
G. E. Climbing the density functional ladder: Nonempiri-
cal meta-generalized gradient approximation designed for
molecules and solids. Phys. Rev. Lett. 91 (2003).
[26] Staroverov, V. N.; Scuseria, G. E.; Tao J.; Perdew, J. P.
Comparative assessment of a new nonempirical density
functional: Molecules and hydrogen-bonded complexes.
J. Chem. Phys. 119, 12129 (2003).
[27] Becke, A. D. Density-functional thermochemistry. III.
The role of exact exchange. J. Chem. Phys. 98, 5648,
(1993).
[28] Weigend, F.; Ahlrichs, R. Balanced basis sets of split
valence, triple zeta valence and quadruple zeta valence
quality for H to Rn: Design and assessment of accuracy.
Phys. Chem. Chem. Phys. 7, 3297 (2005).
[29] Weigend, F. Accurate Coulomb-fitting basis sets for H to
Rn. Phys. Chem. Chem. Phys. 8 1057 (2006).
[30] Ulusoy, I.S.; Vendrell, O. Dynamics and spectroscopy
of molecular ensembles in a lossy microcavity. J. Chem.
Phys. 153, 044108 (2020).
[31] Fischer, E.W.; Saalfrank, P. Cavity-induced non-
adiabatic dynamics and spectroscopy of molecular rovi-
brational polaritons studied by multi-mode quantum
models. J. Chem. Phys. 157, 034305 (2022).
[32] Chen, T.-T.; Du, M.; Yang, Z.; Yuen-Zhou, J.; Xiong,
W. Cavity-enabled enhancement of ultrafast intramolec-
ular vibrational redistribution over pseudorotation. Sci-
ence 378, 794 (2022).
[33] Sidler, D.; Schnappinger, T.; Obzhirov, A.; Ruggen-
thaler, M.; Kowalewski, M.; Rubio, A. Unraveling a
Cavity Induced Molecular Polarization Mechanism from
Collective Vibrational Strong Coupling. arXiv preprint
arXiv:2306.06004 (2023).